A New Type of Chiral Sulfinamide Monophosphine Ligands: Stereodivergent Synthesis and Application in Enantioselective Gold(I)‐Catalyzed Cycloaddition Reactions

Zhang, Zhan‐Ming; Chen, Peng; Li, Wenbo; Niu, Yanfei; Zhao, Xiao‐Li; Zhang, Junliang

doi:10.1002/anie.201401067

Cited by 250 publications

(77 citation statements)

References 60 publications

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“…[4] This is mainly due to the linear coordination geometry of ligand–Au–alkyne and the anti-addition of Au and a nucleophile across the alkyne. To address this problem, both well-defined large chiral ligands [5] and the use of chiral counter anions have been studied with some success. [6] Some of these reactions were rendered enantioselective by using other carbophilic catalysts, such as iridium, [7] platinum, [5c,8] palladium, [9] and copper.…”

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confidence: 99%

“…To address this problem, both well-defined large chiral ligands [5] and the use of chiral counter anions have been studied with some success. [6] Some of these reactions were rendered enantioselective by using other carbophilic catalysts, such as iridium, [7] platinum, [5c,8] palladium, [9] and copper. [10] However, these strategies can only be applied to a limited number of transformations.…”

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confidence: 99%

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Enantioselective Tandem Cyclization of Alkyne‐Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis

Zhu

Wang

et al. 2017

Angew Chem Int Ed

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We report the enantioselective synthesis of tetracyclic indolines using cooperative silver(I) and chiral phosphoric acid catalysis. A variety of alkyne-tethered indoles are suitable for this process. Mechanistic studies suggest that the in situ-generated silver(I) chiral phosphate activates both the alkyne and the indole nucleophile in the initial cyclization step through an intermolecular hydrogen bond and the phosphate anion promotes proton transfer. In addition, further modifications of the cyclization products enabled stereochemistry-function studies of a series of bioactive indolines.

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confidence: 99%

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confidence: 99%

Enantioselective Tandem Cyclization of Alkyne‐Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis

Zhu

Wang

et al. 2017

Angew Chem Int Ed

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“…In 2014, a significant improvement in this methodology came about with introduction of chiral sulfinamide monophosphine (Ming-Phos) ligands. In addition to expanded substrate scope, the authors were able to select for a new product diastereomer [45]. A related reaction via the kinetic resolution of 1-(1-alkynyl)cyclopropyl ketones with nitrones was also demonstrated by the group of Zhang [46].…”

Section: Intermolecular Cycloadditionsmentioning

confidence: 99%

Enantioselective Gold-Catalyzed Synthesis of Heterocyclic Compounds

Miles

Toste

2015

Topics in Heterocyclic Chemistry

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Asymmetric gold-catalyzed syntheses of a diverse range of heterocycles are described herein. This chapter outlines efforts toward the construction of these molecules via intermolecular, intramolecular, and tandem cyclization strategies. Additionally, asymmetric hydrogenation and epoxidation approaches are detailed. These methodologies generally utilize substrates containing soft, unsaturated carbon-carbon bonds, which can easily interact with the carbophilic gold atom(s). Mostly through the use of bis-or monophosphine ligands, modest to excellent yields and enantioselectivities are obtained for a variety of partially and fully saturated heterocycles. Although steric variation of the phosphine catalyst is the most commonly used strategy for enantioinduction, the use of chiral counteranions has proven useful for more challenging transformations. This chapter includes only examples of syntheses where a chiral gold catalyst is used in the direct formation of the heterocycle; examples of pendant functionalization of an existing heterocycle or chirality transfer from enantioenriched substrate to product are not included.

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“…In 2014, the same group reported a class of newly developed chiral sulfinamide monophosphine ligands named Ming‐Phos, which were readily accessed through a modularized synthetic route from commercially available and inexpensive starting materials, 2‐(diphenylphosphino)benzaldehyde and ( R S )‐ tert ‐butanesulfinamide . The above cascade [3+3] cycloaddition was carried out to test the efficiencies of the Ming‐Phos ligands.…”

Section: Tandem Annulations For the Constructions Of Chiral Polycyclimentioning

confidence: 99%

Gold‐Catalyzed Enantioselective Annulations

Zhang

2016

Chemistry A European J

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215

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Non-oxidative,regioselective,and convergent access to densely functionalized oxazoles is realized in af unctional-group tolerant manner using alkynyl thioethers.S ulfur-terminated alkynes provideaccess to reactivity previously requiring strong donor-substituted alkynes such as ynamides.Sulfur does not act in an analogous donor fashion in this gold-catalyzed reaction, thus leading to complementary regioselective outcomes and addressing the limitations of using ynamides. Compared to other heteroatom-substituted alkynes,alkynyl thioethers are remarkably little explored in intermolecular late-transition-metal catalysis,d espite being readily accessed and robust. [1, 2] Ynamides,i nc ontrast, are privileged sub-strates:i np-acid catalysis their donor nature aids metal-alkyne coordination and affords highly polarized electro-philes,t hus providing the high chemo-and regioselectivity required for the discovery of efficient intermolecular reactions (Scheme 1a). [3,4] As the resulting inclusion of ad onor-nitrogen atom limits the utility of the products,r etaining the reactivity profile of these transformations whilst accessing more flexible and readily elaborated substitution patterns would be desirable.T he value of sulfur-substituted compounds [5] coupled with progress in C À Ca nd C-heteroatom bond formation from CÀSbonds, [6] renders alkynyl thioethers appealing alternatives to ynamides.I ndeed the ketenethio-nium pathway (Scheme 1a)f rom alkynyl thioethers has recently been invoked in proton-catalyzed reactions with nitriles [2g,h] and gold-catalyzed reactions with sulfides. [2i] Ynamides enabled the discovery of formal [3+ +2] dipolar cycloadditions with nucleophilic nitrenoids, [7] thus allowing intermolecular access to a-imino gold carbene-type reactivity for heterocycle synthesis (Scheme 1b). [8, 9] Such reactions, which do not depend on ynamides,a re scarce. [8b,h] As trong donor alkyne substituent proved critical in the formation of oxazoles using N-acyl pyridinium N-aminides,aselectron-rich alkynes such as anisole derivatives did not react (Scheme 1b, inset). [8a,b] Oxazoles are valuable synthetic intermediates [10,11] and structural components in bioactive natural products, [12] agrochemicals, [13] ligands, [14] and functional materials. [15] Despite recent advances,asingle modular and convergent route to trisubstituted oxazoles,which provides the structural and functional-group diversity needed across the 2-, 4-, and 5-positions,r emains unrealized. [16] Following our interest in the use of gold catalysis with sulfides [17] we report here on the reactivity of alkynyl thioethers with nucleophilic nitrenoids to prepare oxazoles. Importantly,t he regioselectivity is not consistent with ac on-trolling ketenethionium species.T he sulfur group plays an alternative role in enabling reactivity,t hus proving complementary to donor-enabled approaches. Ther eaction of the alkynyl thioether 1a and aminide 2a (Table 1) showed that conversion into the oxazole 3 was possible at 125 8 8Ci n1 ,2-dichlorobenzene (1,2-DCB;s ...

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A New Type of Chiral Sulfinamide Monophosphine Ligands: Stereodivergent Synthesis and Application in Enantioselective Gold(I)‐Catalyzed Cycloaddition Reactions

Cited by 250 publications

References 60 publications

Enantioselective Tandem Cyclization of Alkyne‐Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis

Enantioselective Tandem Cyclization of Alkyne‐Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis

Enantioselective Gold-Catalyzed Synthesis of Heterocyclic Compounds

Gold‐Catalyzed Enantioselective Annulations

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